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Method Gum Destruotively Sulfate distilled wood Steam and solvent wood Total
Rosin. Turpentine, Pine Oil, Bbl. Bbl. Gal. 1,833,333 23,000 ]4,72:,587 806,000 136,000
f ~ ~ : ~ ~ ~
- 737,000 4,729,587
2,661,333
Not produced by the g u m proceee. b Not produced by the destruotively distilled process.
0
What are these methods? Briefly, the gum process utilizes the oleoresin of living southern pines. Turpentine is obtained from this liquid by distillation, with rosin the residue. The destructively distilled method produces turpentine, pine oil, pine tar oils, pine tar, and charcoal, but no rosin, by furnace baking or retorting of cut lengths of dead wood. Sulfate naval stores are by-products of the sulfate pulping process of the paper industry. The method involves the cooking of the chips in an alkaline solution. Turpentine is recovered from the vapors; the rosin later is difficultly refined from the “curds” of the remaining liquor. The fourth process, the steam and solvent method, was invented in 1906. It consumes shredded wood of southern longleaf pine stumps and produces pine oil, turpentine, and rosin. It is in this latter method that we are interested. It is interesting to touch on the origin of the steam and solvent process. From 1900 to 1910 the Federal Government repeatedly urged inventors and capital to find new sources of naval stores because it was greatly feared that the expected depletion of virgin longleaf stands in the South by lumbering and poor turpentine practices would soon seriously affect production. The Department of Agriculture and other government agencies helped to keep this fear alive, not only in that period, but later during the next decade. Would America lose one of its long-held world-wide markets? Not if American ability could help it, was the answer of private enterprise! Developments were launched all over the country; companies were organized by the dozens for the production of naval stores from the down wood and stumps which cluttered southern cut-over lands. All were destined to fail because of their inefficiency and their inability to make a profit even with generally satisfactory prices. The turpentine price drop in 1909 administered the final blow. Up to 1910 the naval stores industry was usually referred to as the turpentine business, for outside of truly naval stores
* Illustrations, page 686, reading from left to right
T o p row: Giant tractors drag out intact the stumps to be used in the steam and solvent process. No lurking stump escapes these grovels on the stump puller’s “nutcracker.” Second row: Stump wood receives a mechanical baptism at the head of the mill room where a huge orange-peel gra ple dumps onto chain conveyors. In early days, mule-power frought the wood to raibheads-slow, especially in bad weather. Third row: Fire prevention and plant safety methods developed this fireless plant locomotive which fills its boiler stomach every six hours from a steam pipe. Wood at Hattiesburg is bought from contractors and farmers; this farm cash crop is entering the plant.
Bottom row: At railheads today hoists dump baskets of wood, formed by cables, in open gondolas; the trucks are designed with double tires for better traction in muddy acres. T o assure customers of an uninterrupted supply of products, vast reserves of s t u p wood are maintained at the plants.
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uses, rosin was of little value. Many years earlier it actually had been run into streams or into holes dug in the ground which later were searched for and “mined.” Rosin once was considered a rank adulterant in varnish; but beginning with the 1910 decade industrial uses began to be found for it, and from then on we might more correctly refer to the industry as the “rosin business.” One of the methods which showed some promise during the 1900-10 period was a straight steam-distilled process which produced no rosin. From it, only turpentine and pine oil, then considered mainly a medicinal product, were made. Plants using this process failed along with the others in 1909. I n 1906 a process involving steam distillation was evolved which did recover rosin. It was called the “steam and solvent method” and was invented by Homer T. Yaryan, of Toledo, Ohio. He built a plant at Gulfport, Miss., in 1909 and produced 14,307 round barrels of rosin in the 1909-10 12-month season. This plant, the mother of our present steam and solvent industry, had an initial capacity of 100 tons of wood a day. Besides the rosin it produced that year, it also made 1700 barrels of turpentine and 25,000 gallons of pine oil. Although other experimental wood naval stores plants were operating prior to 1909, they all failed, and the Yaryan plant and the Yaryan process were the sole remnants of the attempts to bolster the supposedly diminishing gum naval stores industry. The Yaryan organization constructed another plant a t Brunswick, Ga., in 1911 with a daily wood capacity of 300 tons. The two plants in the 1912-13 season produced 98,000 barrels of rosin and 15,000 barrels of turpentine, besides pine oil which then had practically no important outlets of consumption. In 1913 another drop in turpentine prices closed these two plants, but they were reopened in 1914. I n the following war years much attention was paid to this process, for the demand on Southern timber had again aroused the old fear of exhaustion of gum-producing trees. HERCULES ENTERS THE INDUSTRY
Seeking a place to utilize its excess chemical facilities and armed with latest congressional and trade-investigating organizations’ reports, Hercules Powder Company in 1919 studied the possibilities which existed in the steam and solvent phase of the naval stores business. This was not the company’s first contact with the industry, for its explosives department had sold dynamite for stumping purposes in the naval stores area for several years. However, it was the chemical possibilities of the industry, not the stump blasting phase, that attracted Hercules in this instance. Deciding that government findings were right and that the steam and solvent naval stores process would become a good chemical investment, Hercules purchased the Yaryan interests in 1920 and built a third plant at Hattiesburg, Miss. Before the latter could start operations, another break in prices occurred, so not until 1923 did that plant enter production. To add to Hercules’ price woes, it soon became evident that the gum industry, instead of dying a lingering death, would recover with an overproduction bang. Second-growth slash pine, which had seeded itself in cut-over areas, had reached tapping age. This fast-growing, easily seeding tree proved to be the salvation of the gum industry, for it was found to produce in quantity and quality an oleoresin equal to that of the longleaf type. Inroads by substitutes into avenues of consumption long considered naval stores’ own commenced to shrink naval stores markets. Increased production in other countries also inTHE AMERICAN WAY
(Right) Modern in 1916, this rosin refinery represented the best in the industry.
(Left)The Hattiesburg roan refinery where chemical and mechauicel control produce “tailor-made” pfoducta from the crude rosin bese.
(Right) Early view of the Yaryan plant at Xrunswiek, bought by Hercules in 1919.
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creased the grief of American gum producers and similarly affected wood naval stores. Such was the situation Hercules faced in 1921. No encouragement was derived from persons within or without the industry, including the same government agencies that had sponsored the development of the wood naval stores industry. Said one representative: “The present conditions in the softwood distillation industry do not hold out a large measure of promise for the future.” And another: “The industry is characterized by a large number of commercial failures due to fluctuations in market conditions and mistakes in both chemical and commercial aspects.” Another comment was : “The development of the industry will require very large capital expenditures, certainly without immediate return, and with little chance of a fair ultimate return unless investment in physical properties is followed by chemical research on a scale few companies are equipped to undertake.” That last statement was something for Hercules directors to mull over, but it did not frighten them. Accepting the challenge, Hercules proceeded on its twenty-year battle to put chemistry into the steam and solvent naval stores industry. The development of the steam and solvent wood naval stores industry has proceeded in approximate periods of ten years. 1909 saw the completion of the Yaryan plants. Then followed a decade of operating experience, indefinite sales expansion, and gradual acknowledgment that the products of this wood process must receive the benefits of chemical research and process refinement in order to live. From 1920 to 1930 was a period during which Hercules made outstanding progress in wood-gathering methods, in process advancement, in development of consumption channels, and in product improvements. The 1930’s have seen the research and operating fruits of the previous decade satisfactorily applied, and it can now be said that Hercules steam and solvent naval stores products have arrived chemically and commercially. The accomplishments of the past twenty years are of interest industrially and socially, as well as chemically, for all phases of the business received thorough attention. Personnel relations, for example, were of as much importance to the company as were some of the purely technical problems Hercules faced. These different divisions of work, however, will be discussed separately to mark more clearly the work accomplished. We’ll start with the source of steam and solvent naval stores. JOBS FROM WASTE
I n 1921, after the completion of the Hattiesburg plant and before the closing of the old Gulfport unit, the daily wood capacity of the two, plus that of Brunswick, was 630 tons. Today it is about 1300 tons, a sizable amount of wood to gather when one considers that it is shipped to the plants from points as far away as 125 miles. This does not imply that the supply of wood is becoming scarce, for today sufficient stump supplies exist to run the industry for many years. Twenty years ago this did worry investigators of the steam and solvent, process. I n a Department of Agriculture report, it was urged that developers of the method consider the construction of semiportable processing plants which could be moved from point to point in the stump areas so as to be nearer the sources of supply. T o do so was tempting to early producers, for freight rates and other handling charges were very high. However, the need for quantity production in large unit plants eliminated that possibility; instead, Hercules tackled the problem from the other end by devising more efficient wood gathering methods. The stumps, which constitute the “feed” for Hercules steam and solvent plants, are found in the vast cut-over lands MAY, 1939-Page 589
of Mississippi, Georgia, and Florida. These remnants of lumbering are not useful until ten to fifteen years after cutting. By that time the bark has sloughed off, leaving the heartwood in which the resinous material is concentrated. At the Hattiesburg plant, stumps are purchased from farmers and shippers who bring their loads of wood direct to the plant. The raw material for the Rrunswick unit is gathered mostly by company crews who clear cut-over lands by lease arrangement with the owners. This is chemurgy in the true sense for it utilizes a waste product of the land and creates a cash crop for farmers. Last year a t Hattiesburg alone, $550,000 worth of stumps were bought. Such clearance puts back into production for farm land, for second growth timber production, or for grazing, an average of 125,000 acres annually. In this connection, the comment of the Secretary of Agriculture in 1920 is interesting: “The development of the steam and solvent process will result in increased farming acreage and will help to lower the cost of living. It should be encouraged by all.” Originally, stumps were pulled by mule-power or blasted with dynamite. They were gathered together and hauled by team. With increases in stumping costs, and in lease rights and freight rates, and greater distances to the plants, it was necessary to do yeoman work in lowering costs and increasing efficiency. Today that phase of the business is like a streamlined train in comparison to 1921 methods. The stumps are now pulled by large tractors adapted to the job. After caterpillar tractors gather them into groups and the larger stumps are split by dynamite and trimmed to facilitate handling, the pieces are loaded on trailer trucks which haul them to railheads from whence the cars are shipped to the plants. Besides the resulting reduction in stumping costs and the assurance that greater distances of stumping areas from the plants would not disturb the procurement of a steady supply of wood, the present highly efficient wood gathering method has made more continuous the work of woods camp employees. Adverse weather conditions now have little effect on operations, and even extended rainy periods do not entirely close down work. Some of the innovations and changes for the better, effected by Hercules over original methods in wood gathering, include the change from mules and tram roads (for transporting wood to railheads) to trucks properly equipped to travel over open fields in most kinds of weather. AIso the development of mechanical stump pullers which can travel easily through the cut-over lands removing whole stumps, an improvement over the previous method of blasting which left half the stump deep in the ground. Another change was the use of mechanical cranes for loading stump wood onto truck trailers. Caterpillar tractors were also utilized instead of teams for gathering of pulled stumps into “groups” for splitting and trimming. Originally wood was loaded by hand a t railheads into box cars. Now, large cranes swing bundles of split wood into gondolas of 30 tons capacity. Arriving a t a plant, the long trains of gondolas are shifted to reserve stock pile areas or direct to the plant mill room. I n the latter instance huge grab bucket unloaders swing the wood from cars onto a traveling chain conveyer which transports the feed to the mill room. This system, only recently installed, is a great improvement over the slower, dangerous method of hand unloading. A big impetus was given to the wood naval stores business by the development of a satisfactory i‘hog’l for the reduction of stump wood to properly sized pieces for processing. This hog followed by a shredder now devours irregularly shaped pieces of wood 8 feet long and over a foot thick with no difficulty. The mill THE AMERICAN WAY
rooms of the Hercules plants are marvels in mechanical handling of stump wood. The latest in screen sizing, conveying, and belt weighing are installed. Magnetic “eyes” for the detection of nieces of scraD iron are utilized. These eves automatically ieverse conveiors on which scrap is detected, discharging the offending metal onto a reject pile.
Yields did improve through the years, as indicated by the following estimates of production per ton of wood: Rosin, lb. Total crude oils, gal.
Before 1919 185 6
1921 225 7.5
1938 370 14.0
TREMENDOUS PROGRESS MADE 1921 PRODUCTS UNSATISFACTORY
The present method includes many far-reaching improvements in both the mechanical and chemical phases of the process. These resulted from the years of intensely concerted work of the company’s research, technical service, and operating staffs. Millions of dollars in direct research were expended partly in the main experiment station (first at Kenvil, N. J., and later a t the new one near Wilmington) and a t the plant testing laboratories where much of the work was done. Some of the achievements in plant design and process should be mentioned here. For instance, in the extractor house simultaneous extraction of both turpentine and rosin with a solvent was developed. Heretofore we steamed for turpentine and then leached out the rosin with a solvent. In the refinery a partial separation of oils was effected by sending them through a packed tower without re-evaporation. By providing a better vacuum in the process, improved products were obtained. Of great importance was the Hercules design of vertical evaporators for taking rosins down to dryness. In the still house, fractionating columns, operating under various degrees of pressure and vacuum, were developed to displace the older pot stills. This made possible a clean separation of variously desired cuts. With this facility came a large number of special products which formerly were not available, such as anethol, dipentene, and pinene. One of the greatest achievements was the treatment of turpentine to remove its objectionable odor. These and other important developments widened the markets for Hercules steam and solvent products. Many were distinctly Hercules contributions t o the science of naval stores chemistry, with each extending the naval stores market and adding to employment in the South. It should be emStump Wood phasized that these transitions from the original method inHogged, Shredded, and Steam-Distilled creased the smoothness and control of the process and made it approach more closely one of continuous operation. Not all of the progress Hercules was called on to make was Aqueous Layer Oil Layer of Distillate Wood Extracted with Fractionally SteamPetroleum Distillate of Distillate in manufacturing. Probably the biggest obstacle faced in Discarded Distilled 1919, and the most disheartening, was the poor standing of 1 wood naval stores in the markets. Buyers considered that the 1 quality of the rosin, turpentine, and pine oil was too low to Wood Solution Pine Oil Wood Steamed to Recover Solvent, then Fractionated Turpentir Le interest them. The markets, therefore, were greatly reUsed as Fuel stricted and this prejudice against wood rosin and wood turI pentine stood for many years. Pine oil was still considered I I i a new product for which there was little use. Solvent Rosin Pine Oil
Let us review the status of steam and solvent naval stores products in 1921. There were only the three materials available-rosin, turpentine, and pine oil. Practically no research had been carried out to determine what chemicals could be made from them. I n fact, conditions governing their characteristics-and these were mostly bad-were little known. Little hope was held that much could be done to bring wood products into competitive range with gum or with the increasing number of chemicals that were competitively entering gum naval stores fields. A 1921 commentator said: “Wood rosin is generally E or F in color, which for most purposes is equal to gum of similar or lower (darker) grades. Wood rosin has a characteristic reddish or ruby color; when submitted to high temperatures, it darkens somewhat more than gum and, therefore, is inferior to gum of equal grades.” A government representative reported in 1920: “I hope the industry may improve the process t o make H, t o make rosin harder, and to eliminate viscous matter from it. On pine oil I hope the mineral oil can be removed and that the color can be improved to a t least a straw color.” Hercules Power Company’s research job was easily defined in 1921, for all that was necessary in framing a program was to assemble the long list of objections potential customers had to these so-called substitutes for gum products. As compared to the same products of 1910 plant days, the materials were better, but only slightly so, and little chemical or physical improvement had been effected. The process in 1919 followed closely that used from 1910. As a matter of fact, today’s method is little changed in principle, though it is greatly different in equipment and control. The method used in 1919 was briefly as follows:
I
r
I
I
A
* Illustrations, page 690, reading f r o m left to right
Top row: Rosin-loading end of Brunswick in the early twenties. With chemical progress came plant improvements; note that wood barrels have been replaced by steel “single trippers. Second row: Shredded wood from the mill room is charged into tall extractors where the steam and solvent process works on the ingredients; this is an old type of extractor. The extractor building at Brunswick now uses these stream-lined units. Modern apparatus in the Brunswick refinery evaporates the rosin solution.
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Third row: When the industry was young, this is the way rosin was loaded. In the modern plants, steam-heated channels lead the rosin stream to loading points; the rosin-loading arm crosses the picture above the steel drums; the heads of these drums will be pressed flush after their rosin charges cool. Bottom row: The Hercules Experiment Station near Wilmington, Del., is headquarters for naval stores research and technical service to customers. although much of the progress in process and products devdopment has passed through the plant laboratories (at right). T H E AMERICAN W A Y
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There was justification for the buyer’s attitude toward the products derived from pine wood by the steam and solvent process in 1920. The rosin was dark red and varied greatly in color, melting point, and solubility. Because of its dark color its use was restricted. Its low and uncertain melting point limited or prohibited its use in many industries where dark rosin could be utilized. Its tendency to crystallize and precipitate when dissolved in petroleum oils and vegetable oils likewise decreased its use. As a result of unsatisfactory trials with FF wood rosin, many industrial consumers of rosin objected to all wood naval stores. The prejudice persisted for many years. Steam-distilled (steam and solvent) wood turpentine in 1920 was a poorly refined distillate with a strong penetrating odor and a variable and uncertain distillation range and volatility. Many industrial consumers refused to recognize it as turpentine, insisting that it was turpentine substitute. It did have the advantage of strong solvent power which led to its use as a paint and varnish thinner. However, the strong odor and uncertain quality of steam and solvent wood turpentine in that period caused many industrial consumers to prohibit its use in their products. Steam-distilled pine oil was a true child of the steam and solvent process for recovering naval stores from pine wood. It had not been available before this method came into being, for it is not obtained from the older gum naval stores process. In 1920 pine oil was to a large extent a straight-run distillate; no attempt had been made to fractionate or to purify it to meet certain industrial requirements. It was a new product for which only a few markets had been developed. Some of the problems Hercules faced and the objectives which had to be reached to justify the company’s entrance into the wood naval stores industry have been recited. These embraced three main objectives: (1) improvements in the basic process for deriving wood rosin, wood turpentine, and pine oil from pine stump wood; (2) improvement in the quality of the basic products to enhance their commercial value; and (3) market research and sales development to create and extend commercial outlets. T o put it more simply: we had to improve the quality of rosin, pine oil, and turpentine; and markets for pine oil had to be developed.
* Illuslrutions, page 692, reading from top to bottom
Left: Before Hercules’ production of pale wood rosins, this F grade represented approximately the best wood rosin available; today the finest,,X, is produced. Not nearly the best, this block of N wood rosin denotes the improvement which the pale wood process ma,de in the F grade. This commissary in 01’ Miss’ served its purpose in the days when the naval stores industry was mostly selling “turps.” At Hattiesburg is Hercules’ modern company store and clubhouse. Right: I n the manufacture of pale wood rosin, this type of floating valve measures the flow of an ingredient. Obsolescence in the chemical industry is both a bugbear and a blessing; this scrap pile at Brunswick denotes greater yields, better products. When these cabins were built by Hercules in 1920 they repre-
sented a real advance in camp housing. Hercules’ “White cities” the natives call them. This is one of the company’s new camps where running water, electric lights, playgrounds, and modern bath and toilet conveniences are provided. Two units of one of Hercules’ movable camps. MAY, 1939-Page 593
RESEARCH AS THE KEYSTONE O F IMPROVEMENTS Research directed toward improvement of the process has brought about steady progress. The installation of the fractionating stills of special design by Hercules engineers resulted in a marked improvement in steam-distilled wood turpentine. Today the crude turpentine is fractionated to yield a highquality product that has gained world-wide acceptance in practically all consuming industries. It possesses a pleasant, mild odor, and is uniform in quality. Special treatment of the crude distillate, as well as changes in the method of extraction, aided in bringing about these improvements. With better methods of extraction and distillation, several new products derived from crude turpentine became available. A high-quality dipentene fraction has found wide acceptance as a special solvent and thinner in varnishes and enamel paints. It also enjoys considerable application as a raw material for synthetic resin manufacture. Other terpene hydrocarbons derived from the crude turpentine are separated and used as one of the essential raw materials for the manufacture of “Petrex”,l a synthetic resin base developed by Hercules chemists. Other fractions find application in the reclaiming of rubber, for solvents, and in disinfectants. More recently the preparation of high-grade alpha-pipene for the manufacture of synthetic camphor has been accomplished, and sales to leading manufacturers here and abroad testify to its excellent quality for this purpose. Pine oil has been simgarly improved by means of fractionation and changes in plant processing. Special pine oils are now available with superior color, odor, and other characteristics as required by various consuming industries. Highquality alpha-terpineol is now obtained by fractionation and chemical treatment. Special pine oils, high in terpene alcohols, find use in numerous industries. ROSIN DEVELOPMENTS The development of a process for the manufacture of pale grades of wood rosin is one of the outstanding achievements of Hercules chemists. By means of differential solvents, this pale rosin was produced which was superior to the old grade of rosin once thought to be the best obtainable from wood. This process is particularly interesting because it is believed to be the first application of the principle of differential solution to the purification of low-price chemically intricate materials. This new wood rosin was not only pale in color but was devoid of many other defects which had been associated with prior wood rosin and which had previously limited the market for that product. Contrary t o the old wood rosins, these pale grades actually bleach upon heating. When the announcement was made of the availability of this new type of wood rosin, Thomas Gamble, editor of The hTaval Stores Review, wrote: “The manufacture of this new grade of wood rosin is regarded as the most important development since wood rosin came on the market in 1910.” This development greatly extended the fields for wood rosin so that today the major portion of Hercules wood rosin finds outlets where the FF wood rosin of 1920 could not possibly be employed. With the development of this process of making pale wood came the production of a dark resin known as “Belro.”’ This, too, enjoys applications in specialized fields for which the original FF rosin would not have been suitable. More recently the perfection of a process for manufacturing hydrogenated rosin was accomplished after years of research by Hercules chemists and engineers. This product is far superior to rosin in resistance to oxidation, retention of color, and chemical stability. It is going into fields where rosin is not employed and is thus further extending the market for naval stores. 1
Registered U. 9. Patent Offioe by Hercules Powder
Company.
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Great strides have been made in developing uses for naval stores products by means of sales research and sales service, for this phase of the problem was of paramount importance. This work embraces advertising, technical assistance to consumers, and consumer research. By this means Hercules developed the present market for its turpentine through distributor, jobber, and dealer channels to the ultimate consumer. A.dvertising, technical, and sales assistance, and direct contact with consuming trades were successful in overcoming the resistance of many important consumers resulting from the poor quality of steam-distilled wood turpentine of 1920. It was in this effort that packaged turpentine in small containers was first offered for sale to consumers. Finding markets for pine oil presented a real problem since this product had relatively few established outlets when Hercules entered this field. By direct contact with potential consumers, chemists studied industrial possibilities, and with this knowledge, special pine oils were prepared to meet specific requirements. As a result, diversified markets for pine oil were developed in textile chemicals, flotation oils, essential oils, disinfectants, detergents, insecticides, etc. Research fellowships at leading technical institutions provided a fund of information that not only assisted in establishing new uses for pine oil, but served as distinct contributions to technical improvements in these industries. Much the same approach has been used to advance the sales of wood rosins and related resins. Direct sales service to the consuming trades resulted in the acceptance of wood rosin in many industries where, because of previous prejudice or technical difficulties, wood rosin was formerly prohibited. Today, Hercules rosin enjoys world-wide acceptance in the major rosin-consuming industries, a position gained only because of the improvement in color, solubility, odor, melting point, and general chemical purity. ‘LVinsol”lresin is another product derived from pine stump wood exclusively by Hercules which is fitting into an everwidening field of industrial application. Its low price, large volume, and suitability for purposes entirely outside of the
* Illustrations, page 694 1. Hercules is proud of this machine expert who has been with the organization for seventeen years. There are three boys in his family, and with the encouragement of father and mother, the eldest is studying for his master’s degree in chemistry, the second is a. sophomore in college, and the youngest leads his high school senior class in scholarship. 2. The mother is proud of the three boys who have lived most of their days in Hercules woods camps. 3. Mother, father, and three sons call this cottage home. 4. Typical of what Hercules considers its best product! 5. These youthful residents of Hercules’ Camp Baldwin thrive in the Florida spring sunshine. 6. Woods camp children go by special busses t o schools like this. 7. Starched, ready for the day, is this pensive daughter of a Hercules woods camp employee. 8. They say, “Our husbands work steady for old man Hercules.” 9. Some day he’ll work for the same company his father has been with for many years.
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usual range of rosin make it one of chemistry’s most potentially important raw materials. Technical sales representatives are rendering valuable assistance in adapting it to the needs of consumers in places never thought of before as important outlets for naval stores. PERSONNEL ACCOMPLISHMENTS
In personnel relations work the company has also made progress. One phase of this activity included the housing of woods crews. The woods camps built in 1920 do not stand comparison with today’s construction, but they were a great improvement over the average housing of the areas in which we operated. The views of several of the present woods camps in which Hercules company members live who are employed on wood gathering operations, testify to the advancement made. It should be remembered that these camps have to be movable, and that in no case can they become permanent camp sites. Nevertheless, they provide employees with most conveniences. Busses transport the men to work and their children to schools. In the newest camp cottages are provided with running water and electric lights, and many have bath and toilet facilities. The rent for these houses is at the monthly rate of $2.00 a room or $8.00 for a four-room cottage. Medical service in most places is difficult to obtain, but in Hercules camps the company provides medical care for each man and his family a t $2.00 a month. This service has been available for ten years. The company offers all employees group accident and sickness insurance a t a great saving. It is a point of outstanding interest that 82 per cent of the woods camps personnel have subscribed. Life insurance also is provided a t low rates, and this is subscribed to by 20 per cent of the employees on wages. Bringing our industrial activities into such agricultural districts presented many problems. Turnover is a major labor problem in the southern areas where we operate, but even in the woods camps which often are moved from place to place, 48 per cent of the camp personnel have service records of five years or more. This is eloquent testimony that employees like to be long-time members of the Hercules family. SUMMARY
Hercules Powder Company looks forward with enthusiasm to the future of wood naval stores. With twenty years of experience and intensive research behind it, the company is in an excellent position to continue its utilization of one of Nature’s cheapest sources of organic acids and aromatic hydrocarbons. From these bases it expects to produce additional terpene and rosin derivatives, “tailor-made’) for industrial uses. If there is any merit to be gained for those twenty years of effort, Hercules would wish to claim it on what it has accomplished in producing such tailor-made products. With the completion of its first job, to bring wood products up to gum grades, its second task became the fashioning of these improved materials into diversified and modified forms of industrial chemicals. This treatment is the outstanding development today after centuries of use of these complex compounds in the form in which they happened to occur in nature. In performing these assignments, Hercules has taken an undeveloped industry and brought it to a high state of chemical perfection. It has given the farmers a cash return for worthless stumps and has conditioned thousands of acres of land for the plow and for second-growth timbering. It has provided steady employment in areas where employment possibilities often are almost totally lacking. Hercules is proud that it did this job in the American Way by itself, without benefit of outside help, and in the face of almost insurmountable handicaps. THE AMERICAN WAY
AEROBIC FERMENTATION Effect of Glutathione, Cysteine, and Hydrogen Sulfide GEORGE W. KIRBY, VICTOR DRILL, AND CHARLES N. FREY The Fleischmann Laboratories, Standard Brands Incorporated, New York, N. Y.
S
closed and the sodium sulfide solution was tipped into the yeast-dextrose-potassium acid phosphate mixture. The final volume of liquid in the flasks in all cases was 4 cc.
The experiments were performed a t 30" C . , with the constant-volume type of respirometer (Warburg manometer) ; 5 mg. of baker's yeast (moist weight) and 80 mg. of dextrose were used in a total volume of 4 cc. of 0.1 M potassium acid phosphate a t pH 4.5. The solids content of the yeast was determined in order to report all results on the same unit dry weight of yeast. The flasks used were of about 55-cc. volume and were equipped with two wells and a side arm. The carbon dioxide was removed, and the oxygen uptake was measured by
Hydrogen sulfide, in the absence of other added sulfhydryl compounds, is shown in Table I to stimulate the rate of aerobic fermentation to approximately the anaerobic level. This confirms a similar finding by Negelein (9) and, since this large stimulation does not occur when the hydrogen sulfide is absorbed by lead nitrate, serves as a test of the technique used. In those cases where cysteine or glutathione was added, an odor of hydrogen sulfide could be detected a t the end of the experiment in the Warburg flasks containing no lead nitrate. In those cases where lead nitrate was used to absorb hydrogen sulfide, a definite darkening of the lead nitrate paper was observed. When the hydrogen sulfide is absorbed by lead nitrate, cysteine or glutathione produces only a relatively small stimulation of aerobic fermentation which is far below the anaerobic level. In the case of cysteine there is a decided inhibition of aerobic fermentation during the first 90 minutes of the experiment. However, when the hydrogen sulfide, which is presumably liberated by decomposition of the cysteine or glutathione, is not removed by lead nitrate, aerobic fermentation is stimulated, almost to the anaerobic level.
INCE the isolation of glutathione from yeast and mammalian tissues by Hopkins (I), a number of workers have investigated the effectof this and other sulfhydryl compounds on the metabolism of living cells and on the action of a number of enzymes. Negelein (8) reported that hydrogen sulfide will stimulate the aerobic fermentation of dextrose by yeast to the anaerobic level. Quastel and Wheatley (3) and Runnstrijm et al. (4, 6) reported that cysteine or glutathione will produce a similar stimulation of the aerobic fermentation rate of baker's yeast. In a series of studies on yeast metabolism we have found that the stimulation which has been attributed to cysteine or glutathione is not due to these compounds per se, but to hydrogen sulfide which is formed when either of these compounds is added to a yeast-dextrose solution under certain conditions.
Experimental Method
Discussion of Results
TABLEI. EFFECTOF HYDROQEN SULFIDE, CYSTEINE, AND REDUCED GLUTATHIONB ON THE RATEOF AEROBICFERMENTATIO Total Fermentation COz per Mg. Yeast (Dry Wt.), Cu. Mm. Control Aerobio: no sulfhvdrvl added Aerob/o' Aerobic Aerobio Aerobio Aerobio 5.0 m i . GSH: Aerobio Anaerobic (in NI): no sulfhydryl added
+$+ +
+
30 min. 19 30 105 8
34 16 20 121
placing 0.4 cc. of 20 per cent potassium hydroxide in one well with a paper roll; the hydrogen sulfide formed was absorbed by placing 0.4 cc. of 20 per cent lead nitrate solution in the other well with a paper roll. The figures given for fermentation carbon dioxide in Table I represent the difference between the total carbon dioxide produced and the oxygen uptake, or respiration carbon dioxide. The effect of hydrogen sulfide on the aerobic fermentation of dextrose was studied by placing 1 cc. of sodium sulfide solution, calculated to evolve 15.7 cu. mm. of hydrogen sulfide a t 30" C., in the side arm of the Warburg flask. After a mixing and equilibration period of 20 minutes, the stopcocks were
1 hr. 39 41 229 8 124 40 81 249
1.5 hr. 50
... ...
24 221 67 184 360
2 hr.
... 75 423 ... ... ...
... ...
3 hr. 81 103 611 122 522 159 473 687
4 hr. 90 126 790 219 705 235 652 865
6 hr. 95 136 949 326 924 315 828 1028
It is concluded that the stimulation of aerobic fermentation by cysteine or glutathione, which has been reported by others, is mainly due to hydrogen sulfide arising from the action of yeast on these compounds.
Literature Cited Hopkins, F. G., Biochem. J . , 15, 286 (1921). Negelein, E., Biochem. Z., 165, 203 (1925). Quastel, J. H., and Wheatley, A. H. M., Biochem. J., 26, 2169 (1932).
Runnstrom, J., Runnstrom, A., and Sperber, E., Naturwissenschaften, 25, 540 (1937). Runnstrom, J., and Sperber, E., Nature, 141, 689 (1938).
